Handbook of Metathesis, Volume 1

Catalyst Development and Mechanism

Robert H. Grubbs, Anna G. Wenzel

• Publisher: Wiley-VCH
• Year: 2015
• ISBN:
  9783527693993
• Edition: 2
• Topic: Physical Sciences
• Subtopic: Physical & Theoretical Chemistry

The second edition of the Handbook of Metathesis, edited by Nobel Prize Winner Robert H. Grubbs and his team, is available as a 3 Volume set as well as individual volumes.

Volume 1, edited by R. H. Grubbs together with A. G. Wenzel focusses on Catalyst Development and Mechanism.

The new edition of this set is completely updated (more than 80% new content) and expanded, with a special focus on industrial applications. Written by the "Who-is-Who" of metathesis, this book gives a comprehensive
and high-quality overview. It is the perfect and ultimate one-stop-reference source in this field and indispensable for chemists in academia and industry alike. View the set here - http://www.wiley.com/WileyCDA/WileyTitle/productCd-3527334246.html

Other available volumes:

Volume 2: Applications in Organic Synthesis, Editors: R. H. Grubbs and D. J. O´Leary - http://www.wiley.com/WileyCDA/WileyTitle/productCd-3527339493.html

Volume 3: Polymer Synthesis, Editors: R. H. Grubbs and E. Khosravi - http://www.wiley.com/WileyCDA/WileyTitle/productCd-3527339507.html

Chapter 1
High-Oxidation State Molybdenum and Tungsten Complexes Relevant to Olefin Metathesis

Richard R. Schrock

1.1 Introduction

The first examples of high-oxidation state (“d⁰”) alkylidene and alkylidyne complexes (of tantalum) were published in 1974 and 1975 [1]. Several years of research were required to show that the principles behind tantalum chemistry could be employed to prepare alkylidene and alkylidyne complexes of Mo, W, and Re in their highest oxidation states (counting the alkylidene as a dianionic ligand and the alkylidyne as a trianionic ligand), and that these high-oxidation state complexes, especially those that contain one or more alkoxide ligands, are efficient catalysts for alkene and alkyne metathesis reactions, respectively. This process has been described in previous reviews [2]. Applications of high-oxidation state catalysts for alkene and alkyne metathesis in organic chemistry have also been reviewed [3], although each of these subjects is reviewed again elsewhere in this series in view of the many recent advancements.

This review will focus on isolated and characterized high-oxidation state molybdenum and tungsten alkylidene and metallacyclobutane complexes. Attention will be directed largely toward monoalkoxide pyrrolide (MAP) complexes because they have yielded the majority of new results in the last several years. MAP species have been found to be especially efficient in several Z-selective olefin metathesis reactions, such as homocoupling, cross-coupling, ethenolysis, and ROMP (see Grubbs, Handbook of Metathesis, 2nd Edition, Volume 2, Chapter 7). Most of what is presented here has appeared since a review in 2009 [4].

In the last decade, impressive advances have been made in the synthesis of alkylidene and alkylidyne complexes that contain metals from groups 4 [5] and 5 [5]i,j,m, [6], especially Ti and V, but – except for the ROMP of norbornene by vanadium complexes – group 4 and 5 metals have not shown wide-ranging activity for olefin metathesis. Well-characterized rhenium(VII) complexes are known to be active for metathesis, and many rhenium(VII) alkylidene and alkylidyne complexes have been isolated [2]a, but little attention has been paid to the syntheses of rhenium alkylidene or alkylidyne complexes in the last decade. Theoretical calculations have been carried out on M(X)(CHR′)(Y)(Z) complexes and their reactions with olefins, where X is imido (primarily) or oxo, and Y and Z are monoanionic ligands [7]; the results of these calculations are discussed in Chapter 6. Basic principles of Mo and W olefin metathesis catalysts will be discussed only if the new data have shed light on t...

Table of contents

• Cover
• Title Page
• Copyright
• Table of Contents
• Preface
• List of Contributors
• Chapter 1: High-Oxidation State Molybdenum and Tungsten Complexes Relevant to Olefin Metathesis
• Chapter 2: Alkane Metathesis
• Chapter 3: Diastereocontrol in Olefin Metathesis: the Development of Z-Selective Ruthenium Catalysts
• Chapter 4: Ruthenium Olefin Metathesis Catalysts Supported by Cyclic Alkyl Aminocarbenes (CAACs)
• Chapter 5: Supported Catalysts and Nontraditional Reaction Media
• Chapter 6: Insights from Computational Studies on d0 Metal-Catalyzed Alkene and Alkyne Metathesis and Related Reactions
• Chapter 7: Computational Studies of Ruthenium-Catalyzed Olefin Metathesis
• Chapter 8: Intermediates in Olefin Metathesis
• Chapter 9: Factors Affecting Initiation Rates
• Chapter 10: Degenerate Metathesis
• Chapter 11: Mechanisms of Olefin Metathesis Catalyst Decomposition and Methods of Catalyst Reactivation
• Chapter 12: Solvent and Additive Effects on Olefin Metathesis
• Chapter 13: Metathesis Product Purification
• Chapter 14: Ruthenium Indenylidene Catalysts for Alkene Metathesis
• Index
• End User License Agreement